CN103074498B - With microwave heating from the method for flyash Ore Leaching gallium - Google Patents
With microwave heating from the method for flyash Ore Leaching gallium Download PDFInfo
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- CN103074498B CN103074498B CN201210590728.5A CN201210590728A CN103074498B CN 103074498 B CN103074498 B CN 103074498B CN 201210590728 A CN201210590728 A CN 201210590728A CN 103074498 B CN103074498 B CN 103074498B
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Abstract
The invention discloses the production technology of flotation gallium in a kind of flyash, comprise the following steps: the present invention comprises the steps of a. and takes the flyash of a certain amount of West of Qinghai Province mining industry Tang Hu power plant and add in flotation device, and in flyash, gallium content is 25 g ton；B. in flotation device, add a certain amount of floatation regulator such as waterglass, 18-amine. flotation agent and foaming agent such as No. two oil etc.；C. use one slightly to sweep floatation process and at room temperature carry out flotation；D. obtaining containing the gallium concentrate that gallium grade is 40 g ton, the response rate is 90%.It is relatively low that the present invention solves gallium content in the flyash existed when directly leaching gallium technique in existing flyash, directly acidleach or alkali soaking technology treating capacity are bigger, the leaching liquid measure needed is the biggest, causing cost recovery high, consumption of raw materials is big, the problem that environmental pollution is serious, by utilizing flyash flotation gallium technique, can be in the case of the response rate reduce seldom, pending ore deposit amount reduction by 50%, it is greatly saved leaching cost.
Description
Technical field
Patent of the present invention is the gallium in flyash to be carried out microwave acid dipping go out, and improves gallium leaching rate and the method shortening extraction time.
Background technology
In the earth's crust, gallium is without independent mineral reserve, mainly with dilute scattered form association in other mineral reserve, such as Pb-Zn deposits, cassiterite, aluminium ore etc..Research finds, being also enriched in gallium in the flyash of power plant, in flyash, the content of gallium is at 12 ~ 230g/t, and potential economic worth is the most considerable.According to statistics, China's flyash quantum of output in 2000 reaches 1.5 hundred million t, can extract gallium 1800t ~ 34500t, is based on 4300 yuan/kilogram by price, can create product 77.4 hundred million ~ 1483.5 hundred million yuan.It is therefore seen that, extracting the rare metals such as gallium in flyash can become an important point of economic increase.
The existing technique extracting gallium from flyash mainly uses acid or alkali extract technology.
US4678647 discloses and extracts gallium and the technique of germanium from flyash, and flyash is placed in combustion furnace by this invention, is heated to 1000 DEG C, is passed through air, reacts 30min.By oxidation, making some arsenic, sulfur etc. remove in the form of an oxide, then pass to hydrogen, temperature rises to 1100 DEG C, makes gallium exist with its reduced oxidation state, then leaches with nitric acid, and the gallium of the nearlyest 80% is recycled.Such method technological process is long, and equipment requirements is harsh, consumes energy the hugest, it is difficult to the most industrially implement.CN200810051209.5 discloses " method extracting gallium from flyash ", and this invention is by the flyash direct leaching of hydrochloric acid conventional heating.He Jiazhen reports " technical study reclaiming gallium from flyash " (flyash, 2002(5), 23-26), gallium content is the flyash of 23.6g/t by research report, burning 3h at 550 DEG C, the content of the flyash gallium after burning is 3lg/t, reacts 8h with the hydrochloric acid of 1:1 flyash intermittent stirring after 60 DEG C with burning, leaching gallium content in flyash is 10.9g/t, and leaching rate is 35.2%.
Directly leaching with acid and generally there is reaction length, leaching rate is relatively low, and gallium resource can not get effectively utilizing.
CN200810017872.3 discloses " production technology extracting gallium from flyash and gangue ", this invention will be ground to the flyash of 200 ~ 240 mesh or gangue with sodium carbonate in flyash: sodium carbonate=1:1 ratio mixes, at 800 DEG C of temperature lower calcination 50min, add water, leach 2h and obtain gallium leachate.Zhao Yi reports " experimentation of separating gallium from flyash " (North China power technology, 1998 (1), 35-37), flyash is sintered by this experiment through sodium carbonate or soda lime process, sintering temperature reaches 1100 DEG C, then leaches with sodium carbonate liquor, and leaching yield is 88.79%.Oriol Fonta(Journal
Of Hazardous Materials A, 2007 (139), 413 423), report with the gallium in sodium hydroxide alkali leaching flyash, study and find at 25 DEG C, naoh concentration 0.7 ~ 1M, sodium hydroxide/flyash is 5L/kg, reacts 6h, and the leaching rate of gallium is 60 ~ 86%.
Directly leach with alkali it is generally required to first by alkali and flyash high-temperature roasting, then conventional leaching, such technological equipment investment is big, and energy consumption is huge, does not meets the requirement of energy-saving and emission-reduction.
In flyash, the gallium of about 58% exists with oxide freely, the isomorphous form of 24% is present in inside mineral, 18% is wrapped in Si-Al tetrahedron, conventional acidleach is little for the destruction of mineral, with isomorph or be present in the gallium of inclusion enclave and be difficult to leach smoothly, so that gallium leaching rate is low.Microwave is a kind of new heating technique, is widely used in the leaching of metallic ore.Microwave heating has following features, solid particle can be promoted easily rupturable, expose unsalted surface, and beneficially liquid-solid reaction is carried out；
Microwave heating is that inside and outside is carried out simultaneously, can avoid the internal and external temperature gradient that in traditional heating mode, solid particle exists；Outer the most in addition electric field action, in Leaching Systems, polar molecule can change rapidly direction, carry out vibration at high speed, increase and mutually collide between material, bigger thermal convection current liquid stream is formed around dielectric grain, the generation nitride layer of agitating solution dispersed granules outer layer, Strengthen education course of reaction, shorten extraction time, and then reduce energy consumption.Therefore, leach in the gallium in flyash is expected to reach the short time purpose efficiently leaching gallium with microwave heating acid system, open up a Tiao Xin road for the gallium in extract powder coal ash.
Summary of the invention
The present invention is directed to from flyash conventional acidleach or extraction time length that alkali extraction exists when taking gallium, leaching rate is low or power consumption is big, the problem that equipment requirements is high, the technique of acidleach under proposition microwave, thus shorten extraction time, improve a kind of method of leaching rate.
A kind of microwave heating of the present invention comprises the steps: from the method for flyash Ore Leaching gallium
A. taking 10g flyash and the hydrochloric acid that concentration is 5 ~ 15% is placed in reaction bulb, in flyash, gallium content is 25g/t, or described flyash is fly ash in electric power plant, and gallium content is 12-230 g/t；
B. heat in microwave, 2min is set by microwave controller and reaches 65 ~ 75 DEG C, response time 10 ~ 20min；
C. reacted and liquid in flask has been carried out sucking filtration, filtrate is settled to 250mL, pipetting 3mL solution with pipet, adding 7mL concentration is the HCl solution of 6mol/L, 0.5mL titanium trichloride solution, shake up standing 5min, it is subsequently adding 2mL rhodamine B solution, adds the benzene-acetone soln extraction 5min of 6mL volume ratio 5:1, take supernatant in cuvette, survey it by ultraviolet spectrophotometer and calculate leaching rate at 560nm wavelength absorbance, comparison gallium standard working curve.
Advantages of the present invention and effect:
The extract technology of the present invention is simple, directly soaks ore deposit with hydrochloric acid, it is not necessary to sample ore is carried out calcination process, decreases equipment consumption and energy resource consumption；Extraction temperature is low, and the response time is short, is only 10 ~ 20min under microwave action, is significantly less than the time required for conventional acidleach, reduces energy consumption；Leaching efficiency is high, can reach 84.21% by leaching rate during microwave leaching, far above the leaching rate of conventional acidleach.
Detailed description of the invention
It is further described from the method and technology scheme of flyash Ore Leaching gallium below in conjunction with embodiment microwave heating a kind of to the present invention.
A kind of microwave heating of the present invention comprises the steps: from the method for flyash Ore Leaching gallium
A. taking 10g flyash and the hydrochloric acid that concentration is 5 ~ 15% is placed in reaction bulb, in flyash, gallium content is 25g/t, or described flyash is fly ash in electric power plant, and gallium content is 12-230 g/t；
B. heat in microwave, 2min is set by microwave controller and reaches 65 ~ 75 DEG C, response time 10 ~ 20min；
C. reacted and liquid in flask has been carried out sucking filtration, filtrate is settled to 250mL, pipetting 3mL solution with pipet, adding 7mL concentration is the HCl solution of 6mol/L, 0.5mL titanium trichloride solution, shake up standing 5min, it is subsequently adding 2mL rhodamine B solution, adds the benzene-acetone soln extraction 5min of 6mL volume ratio 5:1, take supernatant in cuvette, survey it by ultraviolet spectrophotometer and calculate leaching rate at 560nm wavelength absorbance, comparison gallium standard working curve.
Further, flyash is directly leached by described extract technology, it is not necessary to flyash is carried out calcination process.
Further, described extract technology is with hydrochloric acid solution as leachate, the gallium in Strengthen education flyash under microwave heating action.
Further, described flyash is fly ash in electric power plant, and gallium content is 12～230 g/t.
Further, the concentration of described hydrochloric acid is 8 ~ 12%；Extraction temperature is 65 ~ 75 DEG C；Solid-to-liquid ratio is 1:4.5 ~ 5.5；Extraction time is 10 ~ 20min.
Further, microwave reactor is general microwave reactor.
Further, microwave heating power regards the adjustment between 50 ~ 500W automatically of leachate temperature.
Further, in described step a, flyash is West of Qinghai Province mining industry Tang Hu power plant sample, is not required to through pulverization process.
Further, in described step b, microwave reactor is the STARTS microwave reactor that MILESTONE company of Italy produces.
Comprise the steps of
A. taking 10g flyash and the hydrochloric acid that concentration is 5 ~ 15% is placed in reaction bulb, in flyash, gallium content is 25g/t, or described flyash is fly ash in electric power plant, and gallium content is 12-230 g/t；
B. heat in microwave, 2min is set by microwave controller and reaches 65 ~ 75 DEG C, response time 10 ~ 20min；
C. reacted and liquid in flask has been carried out sucking filtration, filtrate is settled to 250mL, pipetting 3mL solution with pipet, adding 7mL concentration is the HCl solution of 6mol/L, 0.5mL titanium trichloride solution, shake up standing 5min, it is subsequently adding 2mL rhodamine B solution, adds the benzene-acetone soln extraction 5min of 6mL volume ratio 5:1, take supernatant in cuvette, survey it by ultraviolet spectrophotometer and calculate leaching rate at 560nm wavelength absorbance, comparison gallium standard working curve.
In step a of the present invention, flyash is West of Qinghai Province mining industry Tang Hu power plant sample, is not required to through pulverization process.
In step b of the present invention, microwave reactor is the STARTS microwave reactor that MILESTONE company of Italy produces.
Embodiment 1, mixes 10g flyash (25g/t) with the HCl solution of 50g mass fraction 10% and is placed in flask, then heats in microwave, arranges 2min by microwave controller and arrives 70 DEG C, and the response time is 15min, and leaching rate is 84.21%.
Embodiment 2, mixes 10g flyash (25g/t) with the HCl solution of 50g mass fraction 10% and is placed in flask, then heats in microwave, arranges 2min by microwave controller and arrives 70 DEG C, and the response time is 10min, and leaching rate is 74.74%.
Embodiment 3, mixes the HCl solution of 10g flyash (25g/t) with 50 g mass fractions 10% and is placed in flask, then heats in microwave, arranges 2min by microwave controller and arrives 70 DEG C, and the response time is 20min, and leaching rate is 74.30%.
Claims (8)
1. one kind with microwave heating from the method for flyash Ore Leaching gallium, it is characterised in that described method comprises the steps:
A. taking 10g flyash and the hydrochloric acid that concentration is 5 ~ 15% is placed in reaction bulb, in flyash, gallium content is 25g/t, or described flyash is fly ash in electric power plant, and gallium content is 12-230 g/t；
B. heat in microwave, 2min is set by microwave controller and reaches 65 ~ 75 DEG C, response time 10 ~ 20min；
C. reacted and liquid in flask has been carried out sucking filtration, filtrate is settled to 250mL, pipetting 3mL solution with pipet, adding 7mL concentration is the HCl solution of 6mol/L, 0.5mL titanium trichloride solution, shake up standing 5min, it is subsequently adding 2mL rhodamine B solution, adds the benzene-acetone soln extraction 5min of 6mL volume ratio 5:1, take supernatant in cuvette, survey it by ultraviolet spectrophotometer and calculate leaching rate at 560nm wavelength absorbance, comparison gallium standard working curve.
Microwave heating the most according to claim 1 is from the method for flyash Ore Leaching gallium, it is characterised in that: flyash is directly leached by described extract technology, it is not necessary to flyash is carried out calcination process.
Microwave heating the most according to claim 1 is from the method for flyash Ore Leaching gallium, it is characterised in that: described extract technology is with hydrochloric acid solution as leachate, the gallium in Strengthen education flyash under microwave heating action.
Microwave heating the most according to claim 1 is from the method for flyash Ore Leaching gallium, it is characterised in that: the concentration of described hydrochloric acid is 8 ~ 12%；Extraction temperature is 65 ~ 75 DEG C；Solid-to-liquid ratio is 1:4.5 ~ 5.5；Extraction time is 10 ~ 20min.
Microwave heating the most according to claim 3 is from the method for flyash Ore Leaching gallium, it is characterised in that: microwave reactor is general microwave reactor.
Microwave heating the most according to claim 1 is from the method for flyash Ore Leaching gallium, it is characterised in that: microwave heating power regards leachate temperature and automatically adjusts between 50 ~ 500W.
Microwave heating the most according to claim 3 is from the method for flyash Ore Leaching gallium, it is characterised in that: in described step a, flyash is West of Qinghai Province mining industry Tang Hu power plant sample, is not required to through pulverization process.
Microwave heating the most according to claim 1 is from the method for flyash Ore Leaching gallium, it is characterised in that: in described step b, microwave reactor is the STARTS microwave reactor that MILESTONE company of Italy produces.
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101603259B1 (en) * | 2014-08-28 | 2016-03-15 | 한국전력공사 | Method and apparatus for extracting lithium from coal ashes |
| CN109897960A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院过程工程研究所 | A method of recycling gallium, phosphide element from the waste residue containing gallium, phosphide element |
| CN114212799B (en) * | 2021-12-21 | 2024-03-12 | 黑龙江省能源环境研究院 | Fly ash pretreatment method for molecular sieve preparation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284668A (en) * | 2007-04-12 | 2008-10-15 | 清华大学 | Process for abstracting earth silicon, oxide of alumina and gallium oxide from high-alumina flying ash |
| CN102515220A (en) * | 2011-11-25 | 2012-06-27 | 潘安标 | Method for extracting alumina and gallium oxide from pulverized fuel ash to prepare aluminum oxide nanometer and polymeric ferric silicate sulfate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284668A (en) * | 2007-04-12 | 2008-10-15 | 清华大学 | Process for abstracting earth silicon, oxide of alumina and gallium oxide from high-alumina flying ash |
| CN102515220A (en) * | 2011-11-25 | 2012-06-27 | 潘安标 | Method for extracting alumina and gallium oxide from pulverized fuel ash to prepare aluminum oxide nanometer and polymeric ferric silicate sulfate |
Non-Patent Citations (2)
| Title |
|---|
| 粉煤灰中镓的浸出试验研究;范丽君等;《粉煤灰》;20120229;第10-12、25页 * |
| 粉煤灰酸法提镓探索研究;白光辉等;《应用化工》;20080731;第37卷(第7期);第757-759页 * |
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| ASS | Succession or assignment of patent right |
Owner name: WEST MINE CO., LTD. Free format text: FORMER OWNER: XIBU MINING INDUSTRY GROUP CORP. Effective date: 20130906 |
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Effective date of registration: 20130906 Address after: 810001 No. 54, 52 Avenue, Xining, Qinghai Applicant after: West Mine Co., Ltd. Address before: 810001 No. 54, 52 Avenue, Xining, Qinghai Applicant before: Xibu Mining Industry Group Corp. |
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